Herbicidal compositions



United States Patent 2,693,408 I HERBICIDAL COMPOSITIONS thiazolylchloro olefin is emulsified in aqueous medium by theaid of a dispersingagent or dispersed directly in water. As dispersing and wetting agentsthere may be employed soft or hard sodium or potassium soaps, alkylofthe class are liquids. The solution of the mercapto- 5 ated aromaticsodium sulfonates such as sodium dodecyl John J. DAmico, Charleston, W.Va., assignor to Monbenzene snlfonate, or an amine salt of dodecylbenzene .santo Chemical Company, St. Louis, Mo., a corpora sulfonicacid, alkali metal salts of sulfated fatty alcohols, tion of Delaware Iethlylerlle oxide1 COl'ldClaiatlOl products ofdalkyl phenols or ta oi aswel as 0 er ispersing an wetting agents.

N0 gpp n D cember 8, 1952, The herbicidal activity of the compounds isillustrated Sena! 3241844- application Ito thlelfog'izge of1 lgean andcorn plants.

. I g e mercaptot iazo'y c oro 0e 11 was emulsified in 18 Chums (CLwater and applied to the foliage at the concentration shown in the tablebelow and the effect on the plants re- This invention relates to amethod of destroying vegecorded. It will be noted that the compoundspossess tation and to herbicidal compositions. More particularstrongherbicidal activity of a type which renders them ly it relates toherbicidal compositions containing as an very effective for use asdefoliants. I

a Table Active Ingredient ,222 Bean Corn 0.3 leaves ieda dr1'(z'Benzothiazolyl'memapto)'s'chloro'z'butene" "l v 1.0 plants gleadler afiresa ilb d anddropped r lzglfi liavesdrl rL V 8-( t er nt l ui p 33 32; 535333 3K3; ggggsg m l-(2-13enzothlazolyl-mercapto)-traus-2,3-dichloro-2-butene g Eggggifii 5:3;3-(2-Benzothiazolyl-mercapto)-1-chl0r0-l-pr0pene 0. 3 plants dead, avesdried, plants dead, leaves dried. Zi-(Mlxed ethyl anddimethyl-2-thiazolyl-me'rcapto)-2-chloro-1-pr0pene figgg g gjll lggafial:::.--. F g8; 'i-(Mlxed ethyl and dimcthyl-2 thlazolyl mcrcapto)JFohIQrQQ-butene. g: 3 2 3 32; 2. 2:; mgg aa g 15 a 8: z-(szMethylflthlezolyl-mercapto)-2-chl0r0-l-pr0pen 1.0 no injury moderate injury, 4-4-MethyL2-thiazolyl merca tohZ-chloro-Z-butene 1.0 shght injury. plantsdead. 3- 5-Carbethoxy-4-methyl-2-tiazolylmercapto)-2-chlor0-1-propene... 1.0 severe injury plants dead,leaves dried.3-(5-Carbomethoxy-4-methyl-2-thiazolylmorcapto)'2-chl0r0-lpr0pene1 1.0severe injury, leaves dried. severe injury, leaves dried.4-(5-Oarbobutoxy-4-methyl-Z-thiazolylmercapto)-2-chlor0-2-butene. 1.0moderate injury moderate injury.z-3-tghloro-z-butenyl)-2-mercapto4methyl-5-thiazoly1methy1 ke- 1.0severe injury, leaves dried... plants dead, leaves dried. 2-( ilhloroallylmercapto)-4-methy1-5-thiaz0ly1-methylketOne 1.0 do Do.

essential active ingredient a Z-mercaptothiazolyl chloro 4 As illustratie of the use on cotton, a spray composiolefin, These agents areeffective against a wide variety non containing 0.3% of1-(2benzothiazolylmcrcapto)- of plants including broad leaf plants andgrasses. A 3-chloro-2-butene was applied to the foliage f a plot ofparticular Object of the invention is to provide herbicidal cottonplants. This resulted in drying and dropping of compositions which areeiiective. defoliants. Another the leaves. A further example of aneffective cotton object isto provide compositions for the destruction ofdefoliant is 1-(2 benzothiazolylmercapto)- 4 chloro-2- noxiousvegetation. r butene.

Since the foliage often interfereswith the proper func- Herbicidalactivity was also demonstrated by applicatiouing of mechanicalharvesters, it is important to have tion of the mercaptothiazolyl chloroolefin to the ground effective defoliating agents available. .Inaccordance with before any plants emerg d.- For example application atthis invention it has been discoveredthat foliage is de- 0 the rate ofpounds per acre of 3-(2-benzgthiazoly1- strayed by contact with 2-mercaptothiazolyl chloro olemercapto)-2-chloro-l-propene or3-(2-benzothiazolylmerfins These toxicants may be conveniently appliedin the capto)l--chloro-l-propene resulted in severe injury to rye formof spray containing concentrations of the active grass and beets whenthe plants emerged. However, the ingredient in the range of 0.1% to10.0%.. Uniform effectiveness is greater when applied directly tofoliage application to the foliage of such crop plants as cotton, andthis mode of application is preferred. As indicated beans and corneffects rapid destruction of the foliage. mixtures of the activeingredient may be employed. A The leaves either dry or drop oil or both.Furthermore, further xample of a suita le mixture is the reaction theherbicidal compositions of this invention are also product obtained bycondensing mixed propane chlorides useful for the destruction of weedssuchas wild aster, and sodium mercaptobenzothiazole. Other mercaptowildnapdmgon, sour grass, goldenrod, Queen Annes thiazolyl chloro olefinsthan those specifically mentioned lace, Canadian thistle, dandelion,dock, Johnson grass, above, as for example2-(3-chloro-2,4-hexadienylmerwild onion, pepper weed, smut grass, carpetgrass, plancapto)benzothiazole, may be used for destroying vegetain,bindwecd, lambs-quarter, fextail, shepherds purse, taticn. chickweed,pigweed, ncttles, wildmnstard, wild radish, The invention is furtherillustrated by applying to fowild morning glory, purs'la'n'eand wildcarrot. liage a phytotoxic amount of a compound of the structure For thepreparation of herbicidal compositions the mercaptothiazolyl chloroolefin. maybe dissolved'm a 51% suitable solvent, asvfor example amineral oil fraction,

and the solution emulsified in water. Preferably mineral S oil fractionshaving herbicidal properties are used. In

general these comprise mineral oil fractions high in aromaticconstituents. Other examples are light parafiin where R is a chlorosubstituted l-alkenyl group containbase oil, fuel oil, diesel oil andbunker C fuel oil. Aling less than five carbon atoms or a compound ofthe though the mercaptothiazolyl chloro olefins are insoluble structurein water, they are soluble in most organic solvents. They are usuallysoluble in acetone, chloroform, ethyl alcohol,

ethyl acetate, benzene, ether and heptane.l(2-benzothiazolylmercapto)-trans-2,3-dichloro-2-butene, however,

is insoluble in cold ethyl acetate. This compound is a light yellowsolid, M. P. 43 0., whereas most members so where R represents a chlorosubstituted lower alkenyl group, R represents a lower alkyl group and R"repre- 1 1 3 sents hydrogen, lower alkyl, lower carbalkoxy or lower acylgroups.

The methods for preparing the mercaptothlazolyl chloro olefins aredisclosed in co-pending applications Serial Nos. 265,211 filed January5, 1952; 294,930, filed June 21, 1952, and 316,095, filed October 21,1952, of which the present application is a continuation-in-part.

- It is intended to cover all changes and modifications of the examplesof the invention herein chosen for purposes of disclosure which do notconstitute departures from the spirit and scope of the invention.

What is claimed is:

l. The method of destroying vegetation which comprises applying to thefoliage thereof a phytotoxic amount of a composition comprising as theessential active ingredient a Z-mercaptothiazolyl chloro olefin havingat least one mercaptothiazolyl group and at least one chloro substituentattached to an open chain lower unsaturated hydrocarbon containing atleast one double bond.

2. The method of destroying vegetation which comprises applying to thefoliage thereof a phytotoxic amount of a composition comprising as theessential active ingredient a compound of the structure where R is anunsaturated chloro substituted lower alkenyl group.

3. The method of destroying vegetation which comprises applying to thefoliage thereof a phytotoxic amount of a composition comprising as theessential active ingredient a compound of the structure where R is achloro substituted l-alkenyl group containing less than five carbonatoms.

4. The method of destroying vegetation which comprises applying to thefoliage thereof a phytotoxic amount of a composition comprising as theessential active ingredient a compound of the structure where R" is amember of a group consisting of hydrogen, lower alkyl, lower carbalkoxyand lower acyl groups, R' represents lower alkyl and R represents achloro substituted lower alkenyl group.

5. The method of destroying vegetation which comprises applying to thefoliage thereof a phytotoxic amount of a composition comprising as theessential active ingredient 1- 2-benzothiazolylmercapto-3-ch1oro-2-butene. 6. The method of destroying vegetation whichcomprises applying to the foliage thereof a phytotoxic amount of acomposition comprising as the essential active in gredient 3 -(2benzothiazolylmercapto)- Z-chloro-l-propene.

7. The method of destroying vegetation which comprises applying to thefoliage thereof a phytotoxic amount of a composition comprising as theessential active in gredient 3 -(2benzothiazolylmercapto)-1-chloro-l-propene.

8. The method of destroying vegetation which comprises applying to thefoliage thereof a phytotoxic amount of a composition compnsing as theessential active ingredient 3-(mixed ethyl anddimethyl-Z-thiazolylmercapto -2-chloro-1-propene.

9. The method of destroying vegetation which comprises applying to thefoliage thereof a phytotoxic amount of a composition comprising as theessential active ingredient 4-(mixed ethyl anddimethyl-Z-thiazolylmercap to -2-chloro-2-butene.

10. A herbicidal composition comprising a major proportion of a carrierand as the essential active ingredient a phytotoxic concentration of aZ-mercaptothiazolyl chloro olefin having at least one mercaptothiazolylgroup and at least one chloro substituent attached to an open chainlower unsaturated hydrocarbon containing at least one double bond.

11. A herbicidal composition comprising a major proportion of a carrierand as the essential active ingredient a phytotoxic concentration of acompound of the structure 12. A herbicidal composition comprising amajor proportlon of a carrier and as the essential active ingredient aphytotoxlc concentration of a compound of the structure where R is achloro substituted 1-alkenyl group containing less than five carbonatoms.

13. A herbicidal composition comprising a major proportion of a carrierand as the essential active ingredient a phytotoxic concentration of acompound of the structure RCS\ /CSR R-- N where R" is a member of agroup consisting of hydrogen, lower alkyl, lower carbalkoxy and loweracyl groups, R represents lower alkyl and R represents a chlorosubstituted lower alkenyl group.

14. A herbicidal composition comprising a major proportion of a carrierand as the essential active ingredient a phytotoxic concentration of1-(2-benzothiazolylmercapto) -3-chloro-2-butene.

15. A herbicidal composition comprising a major proportion of a carrierand as the essential active ingredient3-(2-benzothiazolylmercapto)-2-chloro-1-propene.

16. A herbicidal composition comprising a major proportion of a carrierand as the essential active ingredient a phytotoxic concentration of3-(2-benzothiazolylmercapto -l -chloro-l-propene.

17. A herbicidal composition comprising a major proportion of a carrierand as the essential active ingredient a phytotoxic concentration of3-(mixed ethyl and dimethyl-Z-thiazolylmercapto -2-chloro-1-propene.

18. A herbicidal composition comprising a major proportion of a carrierand as the essential active ingredient a phytotoxic concentration of4-(mixed ethyl and dimethyl-Z-thiazolylmercapto)-2-chlor0-2-butene.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,637,646 Kosmin May 5, 1953 2,637,647 Kosmin May 5, 1953

1. THE METHOD OF DESTROYING VEGETATION WHICH COMPRISES APPLYING TO THEFOLIAGE THEREOF A PHYTOTOXIC AMOUNT OF A COMPOSITION COMPRISING AS THEESSENTIAL ACTIVE INGREDIENT A 2-MERCAPTOTHIAZOLYL CHLORO OLEFIN HAVINGAT LEAST ONE MERCAPTOTHIAZOLYL GROUP AND AT LEAST ONE CHLORO SUBSTITUENTATTACHED TO AN OPEN CHAIN LOWER UNSATURATED HYDROCARBON CONTAINING ATLEAST ONE DOUBLE BOND.